DOE OSTI2021
With the advent of powerful computers, first principle calculations have become a robust and reliable tool to complement experiments in the study of materials. First principle calculations such as density functional theory can be used to guide experiments to save time and effort when it comes to new and advanced materials discovery. Study of charge defects in materials and crystal structure prediction are such areas in which density functional theory calculations facilitate the prediction of defect formation energy, charge transition levels and elemental site occupations. Experimentally, studying charge defects requires inferring results from various techniques. Likewise, determining site occupancies for similar elements using experimental techniques is challenging and sometimes impossible. In this work, we study the charged intrinsic and extrinsic defects and defect complexes in phosphorene and determine the site occupancies of Al, Fe and Si in the τ11 phase using density functional theory. In the defect work, we calculate the defect formation energy, charge transition level, binding energies and Stokes shift for vacancy, dopant substitution and dopant-vacancy defect complexes in phosphorene. We found that vacancy defect in phosphorene becomes negatively charged in n-type doping and may passivate the dopants and reduce carrier concentration and mobility. For non-metal dopants in phosphorene, we predict that O, S and Si prefer to form dopant-vacancy complexes removing the vacancy defect states from the band gap. Mn dopant-vacancy defect complex exhibits possibility of switching between two magnetic spin states. Lastly, using density functional theory, we complement the results from neutron powder diffraction to determine the site occupancies of Al and Si in τ11 phase which was used to determine the alloying element to develop a high temperature and low density alloy.